The liquidliquid equilibria of ternary systems composed of water, butane-2,3-diol, and alcohols such as 2-methylbutan-1-ol, 2-ethylbutan-1-ol, and 4-methylpentan-2-ol were studied at two different temperatures (298.15 and 308.15 K). The experimental tie-line data were compared with the compositional data predicted by the NRTL and UNIQUAC models. The distribution ratio and separation factors were calculated to evaluate the extraction efficiencies. Among the three different branched-chain alcohols selected as extractants, 2-methylbutan-1-ol, which has the shortest chain and branch, provided the highest distribution ratios of 0.550.67. The root-mean-square deviation (RMSD) values were calculated for each ternary system, and the average RMSD value was 0.0058, which assures good reliability.